Process of removing aluminum chloride residues from stills



March 23 1926. 1,578,053

A. M D. MOAFEE PROCESS OF REMOVING ALUMINUM CHLORIDE RESIDUES FROM STILLS Filed Dec. 15, 1923 gvvoenhz I alike-z 014 I Patented Ma 192 6.

4 V 1,578,053 .uu rsn sT sMPATENT OFFICE."

ALMEB mcnurrmgcuna, or. roar an'rnugmnxss, assrenon 'ro GULF anrmme oomramr, for rnrsnuaen, PENNSYLVANIA, A conrom-mo'n or runs,

IPRO( ESS' OF REMOVING ALUMINZUM cnnommi, nnsrnons anon STILLS.

Application filed December 13, 1923. Serial No. 680,512.

To all whom it may concern:

' Be it known that .I, JALMER -MGDUFFIE MOAFEE, a citiz en of the United States, re

siding at Port Arthur, in the county .iof Jeffersonjand State ofTexas, haye mv'ented certain new and useful Improvements 1n a Process of Removing Aluminum Chloride Residues from Stills of which the following is a specification. a r

This invention relates-to processes of re; moving aluminum chloride residues from vessels in which aluminum chloride has been used for catalytic treatment or petroleum hydrocarbons and it comprises breaking up such residues into fine particles ofcoky matter and flushing such particles rom the vessel with water, the particles being formed from the residue either by carrying thecatalytic treatmentto such a stage thatstirring mechanism employed will break up the resi-,

. due into such particlesor by. carryingthe treatment to such a stage that a caked -mass of the residues is formedin' "such condition that it can be disintegrated water; and it further comprises more specifically the process of removing aluminum chloride residues from a still in whiclra distillation of pertoleum, hydrocarbons with aluminum chloride has been performed and inwhich the residues are in the jorm of acaked mass, wherein the still, such caked mass and any residual oil are cooled by introduction of relatively cool oil, cooling oil and any residual oil admixed therewith are withdrawn, the cooled caked mass is wetted with water to disintegrate it and the disintegrated particles flushed fromv the still with '.water;- all as more fully-hereinafter set forth and as claimed.

As is well known from certain of my prior patents, the catalytic properties of anhy drous aluminum chloride can be usefully employed in improving lubricating oil and in the conversion of higher boiling petro-' leum oils. such as gas oil or solar oil, into lower boiling oils, such as gasoline and kero- "sene. Various modes of doing this are in -.use'; the way in which the operation is conducted varying with the circumstances and with the products desired. In all cases, however, handling of the residues remaining after such operation 'is a'problem of'some complexity from a commercial point of view;

. Iti-is desirable to remove the residues and clean the vessels with as little labor and in as short a time as possible and without' damageio the vessel and it is equally desirable to conduct the operation under such condition that the, catalytic activity of the alumi# num chloride is utilized to a maximum extents. Under different conditions, depending'upon the character of the oils used and tivity: is not exhausted and/it may be utilized forwarious purposes. It may be used.

for other-catalyticprocesses on it may be sent to recovery apparatus for the purpose of recovering aluminum chloride therefrom.

At other tunes the catalytic process is carleaving a dry residue in ried to a'point I which event there remains a relatively hard mass or: aluminum chloride hydrocarbon- .compounds wh ch is difiicult to remove.

Usually when the process is carried to this point 'such residual material contains, little remaining free or little remaining active aluminum chloride but this is not" neces sarily so.

It is, however, 'best, when the process is carried on lnsuch a 'way' that a relatively hardy coky residue remains, to arrange con djtions so that the activity of the aluminum chloride is" substantially spent.

l Vhenever the catalytic process is conducts ed in such a way that if this relatively .hard 5 residue rema-ins it has been the customto remove such residues from the vessel or still when a distillation processhas been 'per-.

formed) by hand labor and to preserve 'it for recovery of aluminum chloride there from. In addition to the time lost in cooling down the still toa" point where workmen 7 can enter, digging out the material by hand is a time consuming and arduous task. Entrance of worlnnen into the still is also fraught-with danger and this character of work is particularly disagreeable to the laborers.

I have discovered that contrary to what 5 would be expected, no corrosion of the ves- I sel is to be-feared upon treating such relav I'have found "it is advisable tointroduce broken up by-water as described, there are are readily corroded, for some reason, although a solution of aluminum chloride is produced when water comes in contact with the residues, the vessel is not attacked there- 5 by. This may be due to the fact that; the aluminum chloride is bound or masked with vcoke'and that it takes some time for it t9 go into solution in water, or it may be dueto the fact that the presence ofcertain amounts 0 of oil in the residue protects such residue against the water for a sufiicient length of time to prevent the formation of any substantial amounts of hydrochloric acid in the still, or it maybe due to other reasons: But whatever the reason, Ihavet ound that this v relatively hard residue may beflushed from p the vesselhwith water without" an corrosion of the still. Atmost, itlis left with 'a bright pickled surface. s f a When the residu has been disintegrated by the action ofv mec anical means and when the catalytic process has been carri ed on so that the residue is in the form 'of relatively fine particles, these particles can be flushed nflame:

material remains somewhat warm and when the manholes are opened for the introduc-v tion of'the hose, these stalagmites on exposure .toaair may catch fire and ittherefore 1s advantageous to quickly direct against them a strong stre m of water for the purpose of knocking vt em down.

As typical 6f a distillation leaving the character of residue which is disintegrated by water, inaccordance with my process, and

as typical of a process ofcoolinga still and removmgthe residue, the following example willgserve although; is to be understood thatddd not limit my invention to this distillation process preceding the [formation of the resid ue. a a j I In operating with a 1000 barrel still provided with "a stinrr, I charge about 950 barrelof solar'oil' or gas oil of .-to-

Baum; The burners (when such means of firing are used) are then started and thisjoil is heated to from 300 to- 350 F for the purpose ofrdriving off all moisture. I then add barrels of heavy oil, Whloll may well 25 from the still with water. AndI have dis: r be of the same nature as that originally covered more specifically, that when the residues are in th'e' for of a relatively hard caked ,mass, this in ss maybe broken up charged .td the still, having admixed with it sufiicient anhydrous aluminum {chloride to give me from 2 to 3per cent of aluminum upon-wetting with water so that in a relative: chlo ride by weight-on the total charge. This ly short'time, a half hour or less, fine parti .cles are formed and these fine particles may, (be dlushed from the vessel'. withwater.

Breaking up is asort-of spontaneous disin-' tegr'ation to a state of high fineness I It'is advantageous when removmg' resr- 'dues bymy discontinued during the introduction of the rocess that the-residue should mixtu of oil and: aluminum chloride.

- contain relatively small amounts of acti vej-Ordinarily, the :firing is not discontinued aluminum chloride and I have found that as a general rule, the less is the active alu minum chlori e remaining-ifi-the residue at the time sudha hard cake is lfor'g med, the easier and more eificient 'is the a fictionof water in breaking up such a cake.;'j;,., i In cleaning out; the vessel in accordance with my invention, '1 cool'the'vessel'in certa-in ways and provide against .the danger. of fire by taking certain precautions whichare hereinafter describedin the specific example of the way of leanmg a still.- 7 a water under rather hlgh pressure, say from 50 to 75 pounds, not/only-vfor the purpose of supplying alarge quantity in a short time, but also for the purpose of destroying or knockingdown the upwardly'protruding portions of the hard mass in, the still; Frequently; at the end of a distillation process'when the residue is left in suclr. form that it can be portions of the residue adhering to the walls of the still and there are what cmight be termedlaree frozen bubbles over-the surface of the resldue; In fact, at time's'there are what might be called -sjtalagmitesl 4 to 6 1' 1 3; lhi l After the coolingopemtion during this introduction The mixture is then brought to distillation temperature with continuous stirring',"and pronounced activity of the aluminum chloride will be-.'.:

come exhausted in about 24-,to 30 hours. During "the first 8 to 10 hours of the dis 'tillation, the aluminum' chloride and its hydrocarbon compounds with thenoils are apparently dispersed:throughout the mass of oil undergoing distillation, because of the stirring and of the ebullition taking place, but at the end of this time, the aluminum chloride-hydrocarbon compounds settle toward the bottom of thestill. vObservation of the stirring apparatus indicates .this

point. There is a greater resistance to the drags. resistance to the drag-is such'that it is imacter of the distillate coming over. Y'The aluminum chloride, or its combinations with hydrocarbons, settles on the bottom'of the 'still and at this time, with the percentage of aluminumchloride indicated and the amount of solar oil forming the charge,

At the 1 d of 24 to 30 hours, the H .there will be approximately to. per

cent, that is, 100 or'150 barrels, of solar-oil remaining in the still. This residual solar oil is of purer character thanthat ordinarily charged to the still, but is not otherwise materially different. However, since it becomes more or less moist in the subsequent operations, I do not customarily use it'in another charge. a

At the time when distillation is stopped and the activity of aluminum chloride is spentand when the aluminum chloride and the aluminum chloride hydrocarbon com pounds have formed into a relatively hard mass with an overlying layer of the residual solar oil or unconverted oil, I pump in about I back tothe still, in order to bring the oil down to a safe pumping-out temperature, which is around 250 F. When thls temperature .has been reached, a little steam is I introduced at the top of the still and pumpmg out is immediately started. This top steam is to prevent access of air to the still during this pumping out operation. preferably pump this cooling oil, which will ,be admixed with the residual oil in'the still, to a-tank and use .it as cooling oil in a succeeding operation. The excess may be used for fuel oil. If dried, which may readily be accomplished by heating, it'may, hoW- ever be employed ascharge oil fora succeeding operation. It is necessary to have a cooling coil'between the still and the tank to which this oil is pumped, in order to further cool it down to a safe temperature before storing it. e

At this stage of the operation, there remains in the still a hard mass of aluminum chloride-hydrocarbon compounds. I now turn in more steam and open the manheads of the still for the purpose of driving oif gases and vapors antLpreventing explosions. The still now being open, I deliver a stream of cold water under to '7 5 pounds pressure by means of a hose, through one of the manholes (knocking mites) until the mass of aluminum chloride compounds isthoroughly soaked with water. The lower manhole and the tar plug ofthe still are open. so that the excess of. water I drains out. Within a relatively short time, sav, one-half hour or less, the cake or mass of aluminum chloride-hydrocarbon compounds will break up and as the supply of 0 water is continued,-the resultant pulpy mass is flushed out, of the still. At about the time thematerial tends to break up, the drags are again started. This facilitates the discharge of the material through the tar plug. The tar plug maylead to a'sump, from which down the stalag:

the wet material is umped to stora e bins or tanks which prefidrably 'have perforated walls, permitting a rough filtration or seeping away of the water from the residual solid material. At times, there may be .,;scales of material in 'the still around the.

rivets and portions of the drag" a d it is sometimes advantageous to scrape tiese oft" by means of a hand tool. The still is now at a temperature permitting a man to go,

inside.

With a few days of standing the water is sufficiently drained from the carbonaceous solid material to permit its-use as fuel for furnaces, and indeed, it is fine enough to be used in pulverized coal burners. If the coky material is to be-used for other purposes, it is sent to a filter press or a drier.

When the still is clean, the tar plug is closed and the manholes are replaced, and it is ready for another charge. Operating in the way described, with the distillation period consuming about 24 hours, and when I have found it-necessary to recirculate my cooling oil, I have been able to entirely clean the aluminum chloride still and have it in condition for a fresh charge of solar oil in comparatively a short time. 1

In the accompanying drawings I have shown a: still of the character used in a1 umi-.

num chloride distillation-and from which the residues may be removed in accordance with my invention. The view is a vertical section, certain parts being shown in eleva t1on.- 1

In the drawing, 1 indicates the vessel which in this instance is shown as a still mounted upon the fire box 2. The still may be fired in any of the usual ways. 'Thestill is provided with a stirrer 3 having chains or drags 4, such stirrer being '0 erated by the shaft 5, passing through-Stu ng box 6 and operated by means of the gears 7. The stillis provided with manholes 8, 9 and 10, and with the tar lug 11. The tar plug may llO be'operatedby t e lever 12 and handle 13.

means of pipe 17 on which. is located valve In 0 eration, assuming that an aluminum chlori e distillation process has been performed, the residues are left in the form of a more or less solid. mass or cake at aboutthe height of the lowest. point of manhole 10. The depth of the solid mass will vary depending on the amount of aluminum chloride charged and the characterof-the oil, but as a rule it is'on a level or somewhat lower than the lowest point of manhole 10.

vAt this time the stirringmechanism' is frozen in the mass, and thetemperature of the mass may be above 600 F. In order to expedite the cooling of the still about 500 barrels of cold oil are pumped into the still through line 15. If at the end of this operation the contents of the still have not cooled still will have a temperature of around.250

R, which is a safe pumping out'tempera ture. The next operation is to introduce a little top steam-through line 14 to displace vapors in the vapor space of the still. Tar plug 11 is then raised and valve 18.0pened and the oil is pumped out through cooling coils and discharged to a stock tank at a temperature not exceeding the flash point of the oil. 'After all the oil has thus been pumped out of the still, more steam is put in through line 14, and the'manholes 8, Sand 10 are opened. At this time steam w'ill escape through the manholes Sand 9.- Water is then introduced through manhole 10 by means of a hose or the like. Protuberances of residual material are knocked down by means of the water pressure and after about thirty minutes the hard, caked like mass of residual material has thoroughly disintegrated. During this thirty minute period thetar plug 11 and valve 18 have remained open and are )in connection with the pump which is kept in operation from the time water is started in. After about thirt -min utes the stirrer can be started which assists in delivering the disintegrated mass-to the tar plug 11. By continuing a liberal supply.

of water while ope'rating'the stirrer and pumps the entire contents of. the,still are very quickly discharged through tar plug lland delivered to any convenient point.

lVhat I claim is: i

1. The process of removing. aluminum chloride residues .from a vessel in which aluminum chloride hasflbeen used for catalytic treatment "of, petroleum hydrocarbons, which comprises breaking up such residues into particles and flushing such particles from the vessel with water.

2. The process of removing aluminum chloride residues from a vessel. in which aluminum chloride has been used for catalytic treatment of petroleum hydrocarbons, which comprises-breaking up such residues with water to form small particles and flushing such particles from the vessel.

3. The process of removing aluminum chloride residues: frpmj avessel in which aluminum chloride has been used for catalyt ic treatment of petroleum. hydrocarbons,

and inwhich the. residues" are in the form of a caked mass, which comprises *wetting SllCll mass with water to disintegrate it into small particles and flushing such particles from the vessel in the presence of water. 7

4; The process of removing aluminum chloride residues .from a vessel in which aluminum chloride has been used for catalytic treatment of petroleum hydrocarbons, and in which the residues are inthe form of a eaked mass, which comprises cooling suchmass and any remaining oil by introducing relatively 0001 oil, withdrawing the cooling oiland any oiladmixe'd therewith, wetting'the cooled mass with water to disintegrate it into small particles and flushing such particles from the vessel with water.

5. The process of removing aluminumchloride residues from a vessel in which aluminumchloride has been-used for catalytic treatment of petroleum hydrocarbons, and in which the residues sare in the form of a 'caked'mass, whiclf c-omprisesocooling such mass and remaining oil by introducing relatively cool oil, admitting steam to displace inflammable va ors, Withdrawing theeooling oil and any oi admixedtherewith, wetting the cooled mass with water to disintegrate it into small particles and flushing such particles from the vessel with water.

6. The process of removing aluminum chloride residues "from a .still in which aluminum chloride has been used for catalytic treatment of petroleum hydrocarbons, and in which the're'siduesare in the form of a caked mass, which comprises'cooling such mass and remaining oil .by,introducing relatively 'cool oil, admitting steam to displace inflammable vapors, withdrawing the cool into small particles 1 1d flushing such particles from thevessel with water.

7. In the removal of' aluminum chloride residues from a vessel, the process which comprises formin a residue of such a character that it will isintegrat'e into small particles upon wetting with water, wetting the same with water to form such particles and flushing such particles from the vessel "with water.

8. In? the removal oi aluminum chlorideresidues from a still, the-process which comrises forming a hard residue such as would e left upon distillation of "1000' barrels of -1 25.

solar oil with 2 to 3 per cent of aluminum chloride to leave substantially 10 to 1'5'per' cent ofsolar oil in, the still, breaking up such i the 'still with water.

9. The process of removing aluminum 'aQresidue' with water and flushing-it from chloride residues from a still in which aluminum chloride has been 'used for converting higher boiling petroleum hydrocarbons into lower boiling petroleum hydrocarbons and in which the residues are in the form of acaked-mass with upwardly extending protuberances, which comprises directing a stream of water under pressure against such, protuberanc es to knock them down, wetting such mass with water to disintegrate it into fine particles and flushing such particles fromthe still with water. 10. The process of removing aluminum.

chloride residues from a still in which aluminum chloride has been used for converting higher boiling petroleum hydrocarbons into lower boiling petroleum hydrocarbons and in which the residues are in the form of a caked mass which comprises directing Water under pressure against such mass to wet it whereupon it will disintegrate into small rcpa-rticles and flushing such particles from the still with Water.

11. The process of breaking up hard re .sidua arising from the catalytic action of aluminum chloride on oils and of removing num chloride, the step of wetting such residues with water to disintegrate themrinto small particles.

13. The process of removing from the vessel residues resulting from'treatment of petroleum hydrocarbons therein with aluminum chloride, which comprises cooling such residues and then adding water to them while in the vessel to soften them sufficiently to allow flushing from the vessel with water. In testimony whereof, I have hereunto aflixed my signature.

ALMER 'MGDUFFIE MCAFEE. 

